Sulfurized dyes and process of making same.



IE STATES PAEE FFKCE OSWAIJD SGHABIFENBERG AND HERZBERG, SCHfiNEBERG, NEAR BERLIN, GERMANYfASSIG'rNOBS TOA CTIEN GESELLSUHAFT I'll 1t ANILIN EABRIKATION, O]?

, BERL N, nERMAN SULFURIZED DYES PROCESS OF MAKING SAME.

To all {whom it may concern Be it known that we, OSWALD SCHARFEN- nuns and WILH'ELM Hnnznnno, citizens of the German Empire, residing at Schiiueberg, near Berlin, Germany, our post-'ofiice addresses being, respectively, Wartburgstr'asse and Landshuterstrasse 24, S chiineberg, near Berlin, Germany, have invented certain new and useful Improvements in Sulfurized Dyes and Processes of Making Same, of which the following is a specificatlon.

In German Patent 243,545 as Well as in French Patent 432,440 there is described the manufacture of new indophenols Which on the one side contain a special kind of derivatives of1.8-naphthylenediamin, and on the other side the rest of para-aniinophenol or of a derivative thereof. The aforesaid special derivatives of 1.8-naphthylenediamin comprise among others perimidin derivatives of the following general structure:

in Which R means an inorganic substituent. It for instance R means a hydrogen atom the corresponding substance is the well known periinidin itself. If furthermore for instance R means an oxygen atom the diagram represents the dihydro"-perimidon-Q, and if R means a sulfur atom he diagram represents the dihydrothiop erimidon-EZ.

The atorenam'ed new 'indophenols are obtained by condensing the above-named class of heteronuclearic derivatives with quinonechlorimid or its" derivatives or by joint oxidation with para-aminophenol or its derivatives. Now according to our present invention these new indophenols may be con verted into very valuable new dyes containing sulfur by acting with an alkali-polysuL fidcontai'nin'g'a high or low percentage of sulfur; in 'Inanufacturing such new dyes a suitable solvent, such "as alcohol or a suitable diluent, maybe added. As'to the tints ob tained with thenew dyestufis these vary,

,ten erally speaki g from dark green to dark vents.

Specification 61: Letters Patent.

Application filed Itebruary 26, 1912. Sex-12111 10. 679,993.

Patented June so, 1914.

This mass is then heated to boiling for about hours using a reflux condenser, whcreupon the alcohol is eliminated by distillation and the residue diluted with water; the greater part of the new dycstutl remains nn dissolved as a green-black powder and the rest can be isolated in the usual manner. for instance by introducing a current of air. The new dye thus obtained produces on cotton from a bath, containing an allialrsullid, a blackish full green possessing a full shade over hand and a good 'lastncss,

The new dye as above obtained torus in the dry state a dark powder which is insoluble in concentrated sulfuric acid, alcohol benzene, ether and other usual organic so]- It dissolves in a sodium sulfid solution to a gray-green colored solution from which cotton is dyed in the tint. abovegiven.

-T-he new'dyc dissolves also in an alkaline hydro-sulfite solution to a brownish yellow colored solution 'from which by oxidation the magma] dye is formed.

Of course it is obvious that the present invntion no't limited to the foregoing ex ample or to the details given therein. It

may be stated for instance that instead oi":

theindophenolused in the above example another indophenol 01;: the; class defined on pago l of the specification may be employed;

ELI-5 thus for instance from the indophenol derived from 2.6-dichloro para aminophenol and 2-methyl-perimidin a sulfur dye can be obtained which produces on cotton a dark full green possessing a full shade overhand and a good fast-ness, whereas the indophenol derived from dihydrothioperimidone-Q and (lichlorquinone-chlorimid gives a sulfur dye which dyes cotton dull olive green tints. It is obvious that in using such other indophenols the proportions of the ingredients as well as the other special conditions of reaction may be altered in order to obtain the best results. For instance the reaction. may be performed in the presence of a solvent other than alcohol or of a suitable diluent, or other alkali-polysulfids than that named" in the foregoing example. Finally it is to be stated that instead of the indophenols above cited the corresponding leuco compounds -an be used in order to produce the new dyes.

Now what we claim is,

1. The process of manufacturing new sulfur dyes comprising actin with a polysulfid upon indophenols obtainble from a perimidin compound having the following general structure: v

fit

in which R means an inorganic substituent, and from a para-aminophenoL 2. The process of manufacturing new sulfur dyes comprising actin with a polysulfid upon indophenols obtaina le from a perimidin compound having the following general structure:

in which R means a hydrogen atom, and from a para-aminophenol.

3. The process of manufacturing new sulfur dyes comprising acting with a polysulfid upon indophenols obtainable from a perimidin and a para-aminophenol.

4. The process of manufacturing new sulfur dyes, comprising acting with a polysulfid upon the indophenol which derives from perimidin and para-aminopheno].

The hereinbefore-described. manufacture of new sulfur dyes comprising acting with a polysulfid of a high percentage of sulfur in e oresence of a suitable liquid upon the indophenol which derives from perimidin and para-aininophenol.

(3. The process of manufacturing new sulfur dyes, comprising acting with a polysullid of a high percentage of sulfur in the presence of a solvent upon the indophenol which derives from perimidin and paraalninophenol.

7. The hercinbefore-described manufacture of new sulfur dyes, comprising acting with a polysulfid of a high percentage of sulfur in the presence of water and alcohol upon the indophenol which derives from perin'lidin and para-al'ninophenol.

8. The h-ereinl cfore-dcscribed new sulfur dyes being sulfur containing derivatives of indophcnols obtainable from a perimidin compound having the following general structure:

N N W l in which R means an inorganic substituent, and from a para-aminophenol, and which new dyes being in the dry shape when pulverized dark powders insoluble in the usual solvents but being soluble in an alkali sulfid solution to, generally speaking, green solutions and being soluble in an alkaline hydrosulfite solution to, generally speaking, brownyellow solutions, and these new sulfur dyes producin on cotton from a bath containing an allc i sulfid, generally speaking, green tints.

9. The hereinbcfore-described new sulfur dyes being sulfur containing derivatives of indophcnols obtainable from a perimidin compound having the following general structure:

dark powders insoluble in concentrated sulfuric acid alcohol, benzene, ether and the other usual solvents, and being soluble in a sodium sulfid solution to gray-green to blackish green solutions and being soluble in an alkaline hydrosulfite solution to brown ish yellow solutions and these new sulfur dyes producing on cotton from a bath containing an alkali-sulfid, generally speaking,

dark greemto dark olive-gre cn tints.

i new sulfur dye representing a sulfurized de- 10. The hereinbefore described new sulfur d es being sulfur containing derivatives of in ophenols obtainable from a perimidin compound having the following general structure with a green coloration, and d ein cotton escrlbed.

green shades, substantiall as manufacture the 11. As a new article 0 rivative of the indophenol derived from perimidin and para-amino henol, which new dye in the dry sha e w en pulverized is a dark owdcr lnsolu 1e in concentrated sulfuric acid, alcohol, benzene, ether andthe other usual solvents and is soluble in' a sodium sulfid solution to a gray-green solution and is soluble in an alkaline hydrosulfite solution to a brownish-yellow solution, and this new dye producing on cotton from a bath containing an alkali-sulfid a blackish full green possessing a full shade overhand and a good fastness.

In testimony whereof we have hereunto set our hands inprcsence of two subscribing witnesses.

OSWALD SGHARFENBERG.

' WILHELM HERZBERG.

Witnesses:

HENRY HABPER, WOLDEMAR HAUPT. 

